Spray Pyrolysed Zinc Oxide Thin Films : Effects of Doping and Ion Beam Irradiation

In recent years scientists have made rapid and significant advances in the field of semiconductor physics. One of the most important fields of current interest in materials science is the fundamental aspects and applications of conducting transparent oxide thin films (TCO). The characteristic properties of such coatings are low electrical resistivity and high transparency in the visible region. The first semitransparent and electrically conducting CdO film was reported as early as in 1907 [1]. Though early work on these films was performed out of purely scientific interest, substantial technological advances in such films were made after 1940. The technological interest in the study of transparent semiconducting films was generated mainly due to the potential applications of these materials both in industry and research. Such films demonstrated their utility as transparent electrical heaters for windscreens in the aircraft industry. However, during the last decade, these conducting transparent films have been widely used in a variety of other applications such as gas sensors [2], solar cells [3], heat reflectors [4], light emitting devices [5] and laser damage resistant coatings in high power laser technology [6]. Just a few materials dominate the current TCO industry and the two dominant markets for TCO’s are in architectural applications and flat panel displays. The architectural use of TCO is for energy efficient windows. Fluorine doped tin oxide (FTO), deposited using a pyrolysis process is the TCO usually finds maximum application. SnO2 also finds application ad coatings for windows, which are efficient in preventing radiative heat loss, due to low emissivity (0.16). Pyrolitic tin oxide is used in PV modules, touch screens and plasma displays. However indium tin oxide (ITO) is mostly used in the majority of flat panel display (FPD) applications. In FPDs, the basic function of ITO is as transparent electrodes. The volume of FPD’s produced, and hence the volume of ITO coatings produced, continues to grow rapidly. But the current increase in the cost of indium and the scarcity of this material created the difficulty in obtaining low cost TCOs. Hence search for alternative TCO materials has been a topic of active research for the last few decades. This resulted in the development of binary materials like ZnO, SnO2, CdO and ternary materials like II Zn2SnO4, CdSb2O6:Y, ZnSO3, GaInO3 etc. The use of multicomponent oxide materials makes it possible to have TCO films suitable for specialized applications because by altering their chemical compositions, one can control the electrical, optical, chemical and physical properties. But the advantages of using binary materials are the easiness to control the chemical compositions and depositions conditions. Recently, there were reports claiming the deposition of CdO:In films with a resistivity of the order of 10-5 ohm cm for flat panel displays and solar cells. However they find limited use because of Cd-Toxicity. In this regard, ZnO films developed in 1980s, are very useful as these use Zn, an abundant, inexpensive and nontoxic material. Resistivity of this material is still not very low, but can be reduced through doping with group-III elements like In, Al or Ga or with F [6]. Hence there is a great interest in ZnO as an alternative of ITO. In the present study, we prepared and characterized transparent and conducting ZnO thin films, using a cost effective technique viz Chemical Spray Pyrolysis (CSP). This technique is also suitable for large area film deposition. It involves spraying a solution, (usually aqueous) containing soluble salts of the constituents of the desired compound, onto a heated substrate.

Effect of Chromium Doping on the Diffraction Efficiency of Methylene Blue Sensitized PVA/Acrylamide Films

The effect of chromium doping on methylene blue sensitized Poly (vinyl alcohol)/Acrylamide was carried out by varying the ratios of Ammonium dichromate and methylene blue. In the case of films without ammonium dichromate, the diffraction efficiency was found to decrease on storage. On chromium doping the storage life was improved. Interestingly, a self-enhancement in efficiency was observed for a particular ratio of methylene blue and ammonium dichromate.

Engineering the Properties of Indium Sulfide for Thin Film Solar Cells by Doping

In the present work, structural, optical and electrical properties of indium sulfide are tuned by specific and controlled doping. Silver, tin, copper and chlorine were used as the doping elements. In2S3 thin films for the present study were prepared using a simple and low cost “Chemical Spray Pyrolysis (CSP)” technique. This technique is adaptable for large-area deposition of thin films in any required shape and facilitates easiness of doping and/or variation of atomic ratio. It involves spraying a solution, usually aqueous, containing soluble salts of the constituents of the desired compound onto a heated substrate. Doping process was optimized for different doping concentrations. On optimizing doping conditions, we tuned the structural, optical and electrical properties of indium sulfide thin films making them perform as an ideal buffer layer.

Effect of Te doping on thermal diffusivity of Bi2Se3 crystals: A study using open cell photoacoustic technique

An open cell configuration has been employed for the photoacoustic measurement of the thermal diffusivity of undoped Bi2Se3 crystals and Bi2Se3 crystals doped with various concentrations of Te. The amplitude of the photoacoustic signal obtained under heat transmission configuration as a function of chopping frequency is used to evaluate the numerical value of thermal diffusivity, α. Doped samples show a substantial reduction in the value of α compared to undoped samples. The variations in the thermal diffusivity of the doped samples are explained in terms of the phonon assisted heat transfer mechanism. It is seen that α is very sensitive to structural variations arising from doping. The experimentally observed results are correlated with X-ray diffraction studies.

Photoacoustic study of the effect of doping concentration on the transport properties of GaAs epitaxial layers

We report a photoacoustic (PA) study of the thermal and transport properties of a GaAs epitaxial layer doped with Si at varying doping concentration, grown on GaAs substrate by molecular beam epitaxy. The data are analyzed on the basis of Rosencwaig and Gersho’s theory of the PA effect. The amplitude of the PA signal gives information about various heat generation mechanisms in semiconductors. The experimental data obtained from the measurement of the PA signal as a function of modulation frequency in a heat transmission configuration were fitted with the phase of PA signal obtained from the theoretical model evaluated by considering four parameters—viz., thermal diffusivity, diffusion coefficient, nonradiative recombination time, and surface recombination velocity—as adjustable parameters. It is seen from the analysis that the photoacoustic technique is sensitive to the changes in the surface states depend on the doping concentration. The study demonstrates the effectiveness of the photoacoustic technique as a noninvasive and nondestructive method to measure and evaluate the thermal and transport properties of epitaxial layers.

Highly conductive and transparent ZnO thin film using Chemical Spray Pyrolysis technique: Effect of doping and deposition parameters

In the present work we report the preparation details studies on ZnO thin films. ZnO thin films are prepared using cost effective deposition technique viz., Chemical Spray Pyrolysis (CSP). The method is very effective for large area preparation of the ZnO thin film. A new post-deposition process could also be developed to avoid the adsorption of oxygen that usually occurs after the spraying process i.e., while cooling. Studies were done by changing the various deposition parameters for optimizing the properties of ZnO thin film. Moreover, different methods of doping using various elements are also tried to enhance the conductivity and transparency of the film to make these suitable for various optoelectronic applications.

Effect of cobalt doping on the magnetic properties of superparamagnetic g-Fe2O3-polystyrene nanocomposites

Superparamagnetic nanocomposites based on g-Fe2O3 and sulphonated polystyrene have been synthesized by ion exchange process and the preparation conditions were optimized. Samples were subjected to cycling to study the effect of cycling on the magnetic properties of these composites. The structural and magnetization studies have been carried out. Magnetization studies show the dependence of magnetization on the number of ion exchange cycles. Doping of cobalt at the range in to the g-Fe2O3 lattice was effected in situ and the doping was varied in the atomic percentage range 1–10. The exact amount of cobalt dopant as well as the iron content was estimated by Atomic Absorption Spectroscopy. The effect of cobalt in modifying the properties of the composites was then studied and the results indicate that the coercivity can be tuned by the amount of cobalt in the composites. The tuning of both the magnetization and the coercivity can be achieved by a combination of cycling of ion exchange and the incorporation of cobalt

Optimization of pH and Direct Imaging Conditions of Complexed Methylene Blue Sensitized Poly(vinyl chloride) Films

Significant results of our experimental investigations on the dependence of pH on real time transmission characteristics on recording media fabricated by doping PVC with complexed methylene blue are presented. The optimum pH value for faster bleaching was found to be 4×5. In typical applications, the illumination from one side, normal to the surface of this material, initiates a chemical sequence that records the incident light pattern in the polymer. Thus direct imaging can be successfully done on this sample. The recorded letters were very legible with good contrast and no scattering centres. Diffraction efficiency measurements were also carried out on this material.

Plasma Polymerised Organic Thin Films-A Study on the Structural, Electrical and Nonlinear Optical Properties for Possible Applications

This proposed thesis is entitled “Plasma Polymerised Organic Thin Films: A study on the Structural, Electrical, and Nonlinear Optical Properties for Possible Applications. Polymers and polymer based materials find enormous applications in the realm of electronics and optoelectronics. They are employed as both active and passive components in making various devices. Enormous research activities are going on in this area for the last three decades or so, and many useful contributions are made quite accidentally. Conducting polymers is such a discovery, and eversince the discovery of conducting polyacetylene, a new branch of science itself has emerged in the form of synthetic metals. Conducting polymers are useful materials for many applications like polymer displays, high density data storage, polymer FETs, polymer LEDs, photo voltaic devices and electrochemical cells. With the emergence of molecular electronics and its potential in finding useful applications, organic thin films are receiving an unusual attention by scientists and engineers alike. This is evident from the vast literature pertaining to this field appearing in various journals. Recently, computer aided design of organic molecules have added further impetus to the ongoing research activities in this area. Polymers, especially, conducting polymers can be prepared both in the bulk and in the thinfilm form. However, many applications necessitate that they are grown in the thin film form either as free standing or on appropriate substrates. As far as their bulk counterparts are concerned, they can be prepared by various polymerisation techniques such as chemical routes and electrochemical means. A survey of the literature reveals that polymers like polyaniline, polypyrrole, polythiophene, have been investigated with a view to studying their structural electrical and optical properties. Among the various alternate techniques employed for the preparation of polymer thin films, the method of plasma polymerisation needs special attention in this context. The technique of plasma polymerisation is an inexpensive method and often requires very less infra structure. This method includes the employment of ac, rf, dc, microwave and pulsed sources. They produce pinhole free homogeneous films on appropriate substrates under controlled conditions. In conventional plasma polymerisation set up, the monomer is fed into an evacuated chamber and an ac/rf/dc/ w/pulsed discharge is created which enables the monomer species to dissociate, leading to the formation of polymer thin films. However, it has been found that the structure and hence the properties exhibited by plasma polymerized thin films are quite different from that of their counterparts produced by other thin film preparation techniques such as electrochemical deposition or spin coating. The properties of these thin films can be tuned only if the interrelationship between the structure and other properties are understood from a fundamental point of view. So very often, a through evaluation of the various properties is a pre-requisite for tailoring the properties of the thin films for applications. It has been found that conjugation is a necessary condition for enhancing the conductivity of polymer thin films. RF technique of plasma polymerisation is an excellent tool to induce conjugation and this modifies the electrical properties too. Both oxidative and reductive doping can be employed to modify the electrical properties of the polymer thin films for various applications. This is where organic thin films based on polymers scored over inorganic thin films, where in large area devices can be fabricated with organic semiconductors which is difficult to achieve by inorganic materials. For such applications, a variety of polymers have been synthesized such as polyaniline, polythiophene, polypyrrole etc. There are newer polymers added to this family every now and then. There are many virgin areas where plasma polymers are yet to make a foray namely low-k dielectrics or as potential nonlinear optical materials such as optical limiters. There are also many materials which are not been prepared by the method of plasma polymerisation. Some of the materials which are not been dealt with are phenyl hydrazine and tea tree oil. The advantage of employing organic extracts like tea tree oil monomers as precursors for making plasma polymers is that there can be value addition to the already existing uses and possibility exists in converting them to electronic grade materials, especially semiconductors and optically active materials for photonic applications. One of the major motivations of this study is to synthesize plasma polymer thin films based on aniline, phenyl hydrazine, pyrrole, tea tree oil and eucalyptus oil by employing both rf and ac plasma polymerisation techniques. This will be carried out with the objective of growing thin films on various substrates such as glass, quartz and indium tin oxide (ITO) coated glass. There are various properties namely structural, electrical, dielectric permittivity, nonlinear optical properties which are to be evaluated to establish the relationship with the structure and the other properties. Special emphasis will be laid in evaluating the optical parameters like refractive index (n), extinction coefficient (k), the real and imaginary components of dielectric constant and the optical transition energies of the polymer thin films from the spectroscopic ellipsometric studies. Apart from evaluating these physical constants, it is also possible to predict whether a material exhibit nonlinear optical properties by ellipsometric investigations. So further studies using open aperture z-scan technique in order to evaluate the nonlinear optical properties of a few selected samples which are potential nonlinear optical materials is another objective of the present study. It will be another endeavour to offer an appropriate explanation for the nonlinear optical properties displayed by these films. Doping of plasma polymers is found to modify both the electrical conductivity and optical properties. Iodine is found to modify the properties of the polymer thin films. However insitu iodine doping is tricky and the film often looses its stability because of the escape of iodine. An appropriate insitu technique of doping will be developed to dope iodine in to the plasma polymerized thin films. Doping of polymer thin films with iodine results in improved and modified optical and electrical properties. However it requires tools like FTIR and UV-Vis-NIR spectroscopy to elucidate the structural and optical modifications imparted to the polymer films. This will be attempted here to establish the role of iodine in the modification of the properties exhibited by the films

Copper Doped Methylene Blue Sensitized Poly(vinyl alcohol)–Acrylamide Filmsfor Stable Diffraction Efficiency

Copper doped methylene blue sensitized poly(vinyl alcohol) (MBPVA)–acrylamide films were fabricated to improve the storage life of recorded gratings. The films were fabricated using gravity settling method and the copper chloride concentration was optimized as 3:18 10 3 mol/l for a dye concentration of 6:2 10 4 mol/l. The gratings recorded on the optimized film constitution could be stored for months with stable diffraction efficiency (24%) without any chemical or thermal fixing techniques. The resolution of the material is found to be unaffected with the addition of copper chloride.

Fabrication and Characterization of Methylene-Blue-Doped Polyvinyl Alcohol–Polyacrylic Acid Blend for Holographic Recording

A methylene-blue-sensitized polymer blend of polyvinyl alcohol and polyacrylic acid is fabricated and tested for holographic recording. It was found to have good characteristics such as high sensitivity, storage stability, ease of fabrication, and environmental stability. Optimization of the ratio of polyvinyl alcohol polyacrylic acid, the sensitizer concentration, pH, energy, diffraction efficiency measurements, etc., have been done. pH is found to have a great influence on the recovery of the dye in this matrix. The results of experimental investigations into the properties of this new material are reported.

Methylene Blue Doped Polymers:Efficient Media for Optical Recording

Polymer materials find application in optical storage technology, namely in the development of high information density and fast access type memories. A new polymer blend of methylene blue sensitized polyvinyl alcohol (PVA) and polyacrylic acid (PAA) in methanol is prepared and characterized and its comparison with methylene blue sensitized PVA in methanol and complexed methylene blue sensitized polyvinyl chloride (CMBPVC) is presented. The optical absorption spectra of the thin films of these polymers showed a strong and broad absorption region at 670-650 nm, matching the wavelength of the laser used. A very slow recovery of the dye on irradiation was observed when a 7:3 blend of polyvinyl alcohol/polyacrylic acid at a pHof 3.8 and a sensitizer concentration of 4.67 10 5 g/ml were used. A diffraction efficiency of up to 20% was observed for the MBPVA/alcohol system and an energetic sensitivity of 2000 mJ/cm2 was obtained in the photosensitive films with a spatial frequency of 588 lines/mm.

Optimization of pH and Direct Imaging Conditions of Complexed Methylene Blue Sensitized Poly(vinyl chloride) Films

Significant results of our experimental investigations on the dependence of pH on real time transmission characteristics on recording media fabricated by doping PVC with complexed methylene blue are presented. The optimum pH value for faster bleaching was found to be 4×5. In typical applications, the illumination from one side, normal to the surface of this material, initiates a chemical sequence that records the incident light pattern in the polymer. Thus direct imaging can be successfully done on this sample. The recorded letters were very legible with good contrast and no scattering centres. Diffraction efficiency measurements were also carried out on this material.